Polymers prepared from 4,4&#39;-bis[2-(3,4-(dicarboxyphenyl)hexafluoroisopropyl] diphenyl ether dianhydride

ABSTRACT

This invention relates to new fluorine-containing polyimides, polyamide-acids/esters, polyamides, addition polyimides and imide oligomers which exhibit low melting points, better solubilities, low dielectric constants, superior thermal and thermal oxidative stability, and improved processing characteristics. 
     The products of this invention are characterized by the fact that they are derived from 4,4&#39;-bis[2-(3,4-(dicarboxyphenyl)hexafluoroisopropyl]diphenyl ether dianhydride.

FIELD OF THE INVENTION

This invention relates to new fluorine-containing polyimides,polyamide-acids/esters, addition polyimides and imide oligomers whichexhibit low melting points, better solubilities, low dielectricconstants, superior thermal and thermal oxidative stability, andimproved processing characteristics.

BACKGROUND OF THE INVENTION

Polyimides are widely used in the aerospace industry and electronicsindustry, because of their toughness, low density, thermal stability,radiation resistance and mechanical strength. However, it is recognizedthat polyimides are difficult to process. The processing problems arisefrom the insolubility of polyimides in most of the more common solvents.Consequently, products were fabricated from polyamide-acidintermediates, which are more soluble but less stable, and then imidizedto provide the desired end product. The disadvantage of this process isthat the water liberated during the imidization of the polyamide-acidforms undesirable voids or surface irregularities in the final productwhich reduce its mechanical properties.

Another approach is to provide a fully imidized prepolymer havingreactive end groups. In this way, the water formed during imidization isremoved before the final cure of the prepolymer. The resulting polyimideproduct is typically a thermoset plastic. However, the imidizedprepolymers are not as soluble as would be desired.

It has been suggested that polyimides having a singlehexafluoroisopropylidene linking group in the diamine or dianhydridecomonomers have improved solubility properties. Several patents disclosepolyimides prepared from diamines of this type. For example, U.S. Pat.No. 3,356,648 to Rogers discloses polyimides prepared from2,2-bis(4-aminophenyl) hexafluoropropane and2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride; U.S. Pat.No. 3,959,350 to Rogers discloses polyimides prepared from2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane and other diamines; U.S.Pat. No. 4,592,925 to DuPont et al. discloses polyimides prepare from2,2-bis(3-aminophenyl) hexafluoropropane; U.S. Pat. No. 4,111,906 toJones et al. discloses polyimides prepared from2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane; and U.S. Pat. No.4,477,648 to Jones et al. discloses polyimides prepared from2,2-bis[(2-halo-4-aminophenoxy)phenyl] hexafluoropropane and adianhydride including, inter alia,2,2-bis(3,4-dicarhoxyphenyl)-hexafluoropropane dianhydride.

SUMMARY OF THE INVENTION

The present invention seeks to provide polyimides and oligomers havingimproved solubility and processing characteristics by incorporating intothe polymeric chain a novel aromatic dianhydride compound having twohexafluoroisopropylidene linking groups. The dianhydride may becharacterized as having the formula: ##STR1##

The polyimides are prepared by reacting this dianhydride or thecorresponding tetracarboxylic acid or diacid-diester with diamines. Ithas been found that the polyimides of this invention have low dielectricconstants and superior thermal and thermo-oxidative stability.

In another aspect, the invention also provides new monomers, oligomersand their corresponding addition polyimides. The monomers and oligomersare formed by reacting the new dianhydride with diamines and reactiveend-capping compounds such as aromatic ethynyl amines, nadic anhydrides,benzocyclobutene amines, or maleic anhydrides. The resulting imidemonomers and oligomers may then be cured by addition reactions.

In yet another aspect, the invention provides polymer precursorcompositions, epoxy resin hardeners, matrix resins, composites,laminates, films, fibers, adhesives, coatings, photoresists and moldedarticles.

DETAILED DESCRIPTION OF THE INVENTION

The polyimides of this invention may be characterized as havingrecurring groups of the structure: ##STR2## wherein n is the number ofrepeating groups, R is a divalent organic radical, and A is ##STR3##

These polyimides may be prepared by reacting diamines withtetracarboxylic acids or derivatives of the formula: ##STR4## or adianhydride of the formula: ##STR5## wherein A is a radical of formula(2), and R₁ is hydrogen or a monovalent organic radical, preferablyhydrogen. When R₁ is a monovalent organic radical, R₁ is preferably alower (C₁ -C₈) alkyl or substituted alkyl group.

EXAMPLE 1 Preparation of 4,4'-bis[2-(3,4-Dicarboxyphenyl)Hexafluoroisopropyl] Diphenyl Ether Dianhydride

To a stainless steel reactor 4,4'-bis(2-hydroxyhexafluoroisopropyl)diphenyl ether, o-xylene and hydrogen fluoride are charged in a molarratio of at least 1:2:10. The reaction mixture is stirred in the closedreactor under autogenous pressure at temperatures of between 100 and170° C. for 24 to 96 hours. After evaporation of the hydrogen fluorideat 80° C. the contents of the reactor are poured into ice. The organiclayer is then separated, diluted with methylene chloride, and dried overcalcium chloride. After evaporation of the solvent, the crude product istreated with charcoal in chloroform, filtered and recrystallized. The4,4'-bis[2-(3,4-dimethylphenyl)hexafluoroisopropyl]-diphenyl ether has amelting point 139-141° C. The thusly obtained diphenyl ether isdissolved in acetic acid and charged to a glass pressure vessel. Acatalytic amount of a solution of Co(OAc)₂.4H₂ O, Mn(OAc)₂ ·4H₂ O, HBrand acetic acid is added. The reaction mixture is heated up to 180° C.under oxygen at a pressure of 7.5 bar. The exothermic reaction starts atabout 90° C. with oxygen uptake and is finished in 2 hours at 180° C.The reaction product is then treated with a small amount of oxalic aciddihydrate in acetic acid. After heating the mixture to refluxtemperature for 2 hours, the solution is filtered. Acetic acid and waterare distilled off. Acetic acid anhydride is added to the residue and thesolution is heated to 120° C. for one hour. After cooling to roomtemperature, the crystalline product is isolated, washed three timeswith a mixture of acetic acid and its anhydride, and dried in vacuoyielding 4,4'-bis[2-(3,4-dicarboxyphenyl)hexafluoroisopropyl]-diphenylether dianhydride. M.P.168°-170° C.

The tetracarboxylic acids or derivatives of formulae (3) or (4) may bereacted with diamines having a formula:

    H.sub.2 N--R--NH.sub.2                                     (5)

wherein R is a divalent organic radical. Preferably R comprises anaromatic moiety such as a phenylene or naphthalene group which maycomprise substituent halogen, hydroxy or lower alkyl (C₁ -C₆) groups.Preferably R is selected from the group consisting of ##STR6## whereinR₂ is a carbon-carbon bond, --O--, --S--, ##STR7## wherein R₃ is acarbon-carbon bond, --S--, --SO₂ --, --CO--, --CH₂ --, --C₂ H₄ --,##STR8## R₄ is halogen, hydroxy, lower (C₁ -C₆) alkyl, or lower (C₁ -C₆)alkoxy, m is 0 to 4, preferably m is 0, r is 1 to 4, s is 1 to 5, and uis 0 to 6, preferably u is 0.

Illustrative of diamines which are suitable for use in the presentinvention are:

m-phenylene diamine;

p-phenylene diamine;

1,3-bis(4-aminophenyl) propane;

2,2-bis(4-aminophenyl) propane;

4,4'-diamino-diphenyl methane;

1,2-bis(4-aminophenyl) ethane;

1,1-bis(4-aminophenyl) ethane;

2,2'-diamino-diethyl sulfide;

bis(4-aminophenyl) sulfide;

2,4'-diamino-diphenyl sulfide;

bis(3-aminophenyl) sulfone;

bis(4-aminophenyl) sulfone;

4,4'-diamino-dibenzyl sulfoxide;

bis(4-aminophenyl) ether;

bis(3-aminophenyl) ether;

bis(4-aminophenyl) diethyl silane;

bis(4-aminophenyl) diphenyl silane;

bis(4-aminophenyl) ethyl phosphine oxide;

bis(4-aminophenyl) phenyl phosphine oxide;

bis(4-aminophenyl)-N-phenylamine;

bis(4-aminophenyl)-N-methylamine;

1,2-diamino-naphthalene;

1,4-diamino-naphthalene;

1,5-diamino-naphthalene;

1,6-diamino-naphthalene;

1,7-diamino-naphthalene;

1,8-diamino-naphthalene;

2,3-diamino-naphthalene;

2,6-diamino-naphthalene;

1,4-diamino-2-methyl-naphthalene;

1,5-diamino-2-methyl-naphthalene;

1,3-diamino-2-phenyl-naphthalene;

4,4'-diamino-biphenyl;

3,3'-diamino-biphenyl;

3,3'-dichloro-4,4'-diamino-biphenyl;

3,3'-dimethyl-4,4'-diamino-biphenyl;

3,4'-dimethyl-4,4'-diamino-biphenyl;

3,3'-dimethoxy-4,4'-diamino-biphenyl;

4,4'-bis(4-aminophenoxy)-biphenyl;

2,4-diamino-toluene;

2,5-diamino-toluene;

2,6-diamino-toluene;

3,5-diamino-toluene;

1,3-diamino-2,5-dichloro-benzene;

1,4-diamino-2,5-dichloro-benzene;

1-methoxy-2,4-diamino-benzene;

1,4-diamino-2-methoxy-5-methyl-benzene;

1,4-diamino-2,3,5,6-tetramethyl-benzene;

1,4-bis(2-methyl-4-amino-pentyl)-benzene;

1,4-bis(1,1-dimethyl-5-amino-pentyl)-benzene;

1,4-bis(4-aminophenoxy)-benzene;

o-xylylene diamine;

m-xylylene diamine;

p-xylylene diamine;

3,3'-diamino-benzophenone;

4,4'-diamino-benzophenone;

2,6-diamino-pyridine;

3,5-diamino-pyridine;

1,3-diamino-adamantane;

3,3'-diamino-1,1'-diadamantane;

bis(4-amino-cyclohexyl) methane;

1,5-diamino-pentane;

1,6-diamino-hexane;

1,7-diamino-heptane;

1,8-diamino-octane;

1,9-diamino-nonane;

1,10-diamino-decane;

1,7-diamino-3-methyl-heptane;

1,7-diamino-4,4-dimethyl-heptane;

2,11-diamino-dodecane;

1,3-bis(3-aminopropoxy) ethane;

1,3-diamino-2,2-dimethyl-propane;

1,6-diamino-3-methoxy-hexane;

1,6-diamino-2,5-dimethyl-hexane;

1,7-diamino-2,5-dimethyl-heptane;

1,9-diamino-5-methyl-nonane;

1,4-diamino-cyclohexane;

2,5-diamino-1,3,4-oxadiazole;

N-(3-aminophenyl)-4-aminobenzamide;

4-aminophenyl-3-aminobenzoate;

2,2-bis(4-aminophenyl) hexafluoropropane;

2,2-bis(3-aminophenyl) hexafluoropropane;

2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane;

2,2-bis[4-(2-chloro-4-aminophenoxy)phenyl] hexafluoropropane;

1,1-bis(4-aminophenyl)-l-phenyl-2,2,2-trifluoroethane;

1,1-bis[4-(4-aminophenoxy)phenyl]-l-phenyl-2,2,2-trifluoroethane;1,

4-bis(3-aminophenyl)buta-l-ene-3-yne;

1,3-bis(3-aminophenyl)hexafluoropropane;

1,5-bis(3-aminophenyl)decafluoropentane; and

mixtures thereof.

A mixture of at least two suitable diamines may be reacted with atetracarboxylic acid or derivative of formulae (3) or (4) to producecopolyimides.

Preferred polyimides are those prepared from the tetracarboxylic acidsor derivatives of formulae (3) or (4) and diamines such as2,2-bis(4-aminophenyl) hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-phenyl]hexafluoropropane,bis(4-aminophenyl) ether, m-phenylene diamine and p-phenylene diamine.

A preferred process for preparing the polyimides of this inventioninvolves first preparing a polyamide-acid by reacting the diamine andthe tetracarboxylic acid or derivative such as the dianhydride in anorganic solvent, preferably under substantially anhydrous conditions fora time and at a temperature sufficient to provide at least 50% of thecorresponding polyamide-acid, and then converting the polyamide-acid tothe polyimide. Suitable conditions for reacting the diamine and thedianhydride are disclosed in detail in U.S. Pat. Nos. 3,356,648 and3,959,350, both to Rogers, which are incorporated herein by reference.The intermediate polyamide-acid may also be esterified to providepolyamide-esters.

The polyamide-acids/esters may be characterized as having recurringgroups of the structure: ##STR9## wherein n is the number of repeatinggroups, A is a tetravalent radical of formula (2), R is a divalentorganic radical as defined above and R' is hydrogen or a monovalentorganic radical. In addition to being useful to produce polyimides, thepolyamide-acids may be esterified with thermally polymerizable orphotopolymerizable compounds such as olefinically unsaturatedmonoepoxides to produce polyamide-esters useful in photoresistcompositions.

The polyamide-acids/esters may be cyclicized to form polyimides.Conversion to the polyimides may be accomplished by a heat treatment, achemical treatment or both as described in the above-referenced Rogerspatents.

In a preferred process for preparing the polyimides, the diamine anddianhydride are reacted in gamma-butyrolactone (BLO), or a mixture ofBLO and another solvent such as diglyme. The resulting product is apolyamide-acid which is then converted to the desired polyimide by oneof several methods: heating the polyamide-acid solution untilimidization is substantially complete; or by combining thepolyamide-acid solution and a dehydrating agent, with or withoutcatalyst, and optionally heating the resulting mixture until imidizationis substantially complete. The use of the BLO solvent provides severaladvantages in that it avoids the formation of complexes of thepolyamide-acid and the solvent that typically occur when solvents suchas N-methyl pyrrolidone (NMP) are used and allows the removal of thesolvent to proceed at lower temperatures (below 250° C.) to obtainuniform films. When mixed with diglyme, the ratio by volume of BLO todiglyme is preferably in the range of about 10:90 to 90:10, morepreferably of about 40:60 to 60:40.

The following examples are illustrative of the invention:

EXAMPLE 2

To a 250 ml reaction unit fitted with a condenser, thermometer, stirrerand nitrogen blanket, and purged with nitrogen, 6.68 g (0.02 moles) of2,2-bis(4-aminophenyl) hexafluoropropane (hereinafter "6F-44") arecharged along with 25 g of distilled N-methyl pyrrolidone (NMP) undernitrogen atmosphere. The mixture is stirred to get a clear solution. Tothe clear, very pale yellow color solution, 15.24 g (0.02 moles) of4,4'-bis[2-(3,4-dicarboxyphenyl) hexafluoroisopropyl] diphenyl etherdianhydride (hereinafter "12F-DA") are charged while stirring iscontinued. 63 g of NMP are added to the reaction mixture which is thenstirred overnight at room temperature. The resulting polyamic acid hasinherent viscosity of 0.60 dl/g, measured at 0.5 g/dl at 25° C. indimethyl acetamide (DMAc). 26.4 g of acetic anhydride and 2.65 g of3-picoline are added to 102.61g of the polyamic acid solution. Thereaction is stirred at room temperature for about six hours and theresulting polyimide is precipitated in methanol, isolated by filtration,washed with fresh methanol, and dried overnight in a vacuum oven at 85°C. It is soluble in acetone, DMAc, diglyme, MEK, NMP, THF, chloroform,BLO solvents.

A film is prepared from a solution comprising 20% by weight solids in a50/50 mixture by volume of BLO/diglyme and cured to 350° C. by stepwiseheating. A very pale yellow, clear, flexible, self-supporting, toughfilm is obtained. Its glass transition temperature (T_(g)) is 263° C. bydifferential scanning calorimetry (DSC) and 5% weight loss is at 527° C.by thermal gravimetric analysis (TGA). Tensile strength is about 11300psi at room temperature. Tensile modulus is about 270 Ksi at roomtemperature, elongation at break is about 8% at room temperature, and ithas a limiting oxygen index of 48.

EXAMPLES 3-8

Polyimides are prepared in accordance with the procedure set forth inExample 2 by reacting the 12F-DA dianhydride with the followingdiamines:

2,2-bis(3-aminophenyl) hexafluoropropane (6F-33),

2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (BDAF),

bis(4-aminophenyl) ether (ODA),

o-tolidine (DDMB),

m-phenylene diamine (mPDA), and

p-phenylene diamine (pPDA).

The properties of the resulting polyimides are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________    Example Number    3   4   5   6    7    8                                     Dianhydride       6F-33                                                                             BDAF                                                                              ODA DDMB mPDA pPDA                                  __________________________________________________________________________             Units                                                                Ratio of millimole/                                                                             20/20                                                                             20/20                                                                             25/25                                                                             30/30                                                                              30/30                                                                              12.5/12.5                             12F-DA/  millimole                                                            Diamine                                                                       Inherent dl/g at  0.41                                                                              0.64                                                                              0.57                                                                              0.66 0.65 0.51                                  Viscosity                                                                              25° C. in DMAc                                                (Polyamic Acid)                                                               Inherent dl/g at  0.35                                                                              0.57                                                                              0.49                                                                              0.52 0.40 0.44                                  Viscosity                                                                              25° C. in DMAc                                                (Polyimide)                                                                   Glass Transi-                                                                          °C.                                                                             226 233 254 N/D  260  268                                   tion Temp. (Tg)                                                               5% Weight loss                                                                         °C.                                                                             520 525 520 500  524  531                                   in air (TGA)                                                                  Tensile Strength                                                                       psi      7,400                                                                             9,200                                                                             13,700                                                                            17,100                                                                             15,500                                                                             13,200                                at room temp.                                                                 Tensile Modulus                                                                        Ksi      360 280 280 410  340  270                                   at room temp.                                                                 Elongation at                                                                          %        2.7 10.9                                                                              8.9 6.2  8.3  12.0                                  break                                                                         __________________________________________________________________________

The polyimides exhibit good solubility properties in solvents such asN-methyl pyrrolidone (NMP), dimethyl acetamide (DMAc), diglyme,methylethylketone (MEK), tetrahydrofuran (THF), acetone, chloroform,butyrolactone (BLO), dimethylsulfoxide (DMS), dimethylformamide (DMF)and the like.

The polyimides of this invention may be molded using standard techniquessuch as compression molding or injection molding to produce meltfabricated articles such as safety masks, windshields, electroniccircuit substrates, airplane windows or the like. They may be compoundedwith graphite, graphite fiber, molybdenum disulphide or PTFE for theproduction of self-lubricating wear surfaces useful for piston rings,valve seats, bearings and seals. They may also be compounded with fiberssuch as glass, graphite or boron fibers to produce molding compounds forhigh strength structural components such as jet engine components. Thepolyimides may also be compounded with friction materials to producemolding compounds for high temperature braking components or withabrasive materials such as diamonds for high speed grinding wheels.

The polyimides may be cast as films useful as wire and cable wraps,motor slot liners or flexible printed circuit substrates. They may beused as coatings on substrates such as aluminum or silicone dioxide.They are also useful to produce high temperature coatings for magneticwire, dip coatings for various electronic components, protectivecoatings over glass, metal and plastic substrates, wear coatings, andphotoresist coatings useful in microelectronic processing.

The polyimides may also be used to produce high temperature adhesivesfor bonding aerospace structures or electrical circuitry, conductiveadhesives when mixed with conductive fillers such as silver or gold formicroelectronic applications, or adhesives for glass, metal or plasticsubstrates.

They may be used as varnish compositions or matrix resins to producecomposites and laminates. The varnish compositions and matrix resins maybe used to impregnate glass or quartz cloth, or graphite or boronfibers, for the production of radomes, printed circuit boards,radioactive waste containers, turbine blades, aerospace structuralcomponents or other structural components requiring high temperatureperformance, non-flammability and excellent electrical properties.

The invention also provides new copolyamideacids/esters andcopolyimides. The copolymers are prepared by reacting diamine of formula(5) with a mixture of at least one tetracarboxylic acid or derivative offormulae (3) or (4) and at least one tetracarboxylic acid or esterhaving t he formula: ##STR10## or dianhydride having the formula:##STR11## wherein B is a tetravalent organic radical having at least 4carbon atoms and R₁ is as defined above. Preferably B comprises anaromatic moiety such as a phenylene or naphthalene group which maycomprise substituent halogen, hydroxy or lower (C₁ -C₆) alkyl or lower(C₁ -C₆) alkoxy groups.

Preferably B is selected from the group consisting of: ##STR12## whereinR₅ is a carbon-carbon bond, --O--, --S--, ##STR13## wherein R₆ is acarbon-carbon ##STR14## R₄ is halogen, hydroxy, lower (C₁ -C₆) alkyl orlower (C₁ -C₆) alkoxy, m is 0 to 3, preferably m is 0, r is 1 to 4, ands is 1 to 5.

Illustrative of tetracarboxylic acid dianhydrides which are suitable foruse in the present invention are:

1,2,4,5-benzene tetracarboxylic acid dianhydride;

1,2,3,4-benzene tetracarboxylic acid dianhydride;

1,4-bis(2,3-dicarboxyphenoxy) benzene dianhydride;

1,3-bis(3,4-dicarboxyphenoxy) benzene dianhydride;

1,2,4,5-naphthalene tetracarboxylic acid dianhydride;

1,2,5,6-naphthalene tetracarboxylic acid dianhydride;

1,4,5,8-naphthalene tetracarboxylic acid dianhydride;

2,3,6,7-naphthalene tetracarboxylic acid dianhydride;

2,6-dichloronaphthalene-l,4,5,8-tetracarboxylic acid dianhydride;

2,7-dichloronaphthalene-l,4,5,8-tetracarboxylic acid dianhydride;

2,3,6,7-tetrachloronaphthalene-l,4,5,8-tetracarboxylic acid dianhydride;

3,3',4,4'-diphenyl tetracarboxylic acid dianhydride;

2,2',3,3'-diphenyl tetracarboxylic acid dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy)diphenyl dianhydride;

bis(2,3-dicarboxyphenyl) ether dianhydride;

4,4'-bis(2,3-dicarboxyphenoxy) diphenyl ether dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy) diphenyl ether dianhydride;

bis(3,4-dicarboxyphenyl) sulfide dianhydride;

4,4'-bis(2,3-dicarboxyphenoxy) diphenyl sulfide dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride;

bis(3,4-dicarboxyphenyl) sulfone dianhydride;

4,4'-bis(2,3-dicarboxyphenoxy) diphenyl sulfone dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride;

3,3',4,4'-benzophenone tetracarboxylic acid dianhydride;

2,2',3,3'-benzophenone tetracarboxylic acid dianhydride;

2,3,3',4'-benzophenone tetracarboxylic acid dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy) benzophenone dianhydride;

bis(2,3-dicarboxyphenyl)methane dianhydride;

bis(3,4-dicarboxyphenyl)methane dianhydride;

1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride;

1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride;

1,2-bis(3,4-dicarboxyphenyl)ethane dianhydride;

2,2-bis(2,3-dicarboxyphenyl)propane dianhydride;

2,2-bis(3,4-dicarboxyphenyl)propane dianhydride;

2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride;

2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride;

4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2propanedianhydride;

2,2-bis[4-(3,4-dicarboxyphenoxy-3,5-dimethyl)phenyl]propane dianhydride;

1,2,3,4-butane tetracarboxylic acid dianhydride;

1,2,3,4-cyclopentane tetracarboxylic acid dianhydride;

2,3,4,5-thiophene tetracarboxylic acid dianhydride;

2,3,4,5-pyrrolidine tetracarboxylic acid dianhydride;

2,3,5,6-pyrazine tetracarboxylic acid dianhydride;

1,8,9,10-phenanthrene tetracarboxylic acid dianhydride;

3,4,9,10-perylene tetracarboxylic acid dianhydride;

2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride;

1,3-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride;

1,1-bis(3,4-dicarboxyphenyl)-l-phenyl-2,2,2-trifluoroethane dianhydride;

2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride;

1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl]-l-phenyl-2,2,2-trifluoroethanedianhydride; and mixtures thereof.

Preferably, the molar ratio of tetracarboxylic acid or derivative offormulae (3) or (4) to tetracarboxylic acid or derivative of formulae(7) or (8) is in the range of from about 10:90 to about 99:1, morepreferably of from about 50:50 to about 99:1. The diamines of formula(5) are suitable for the preparation of the copolymers of thisinvention. The copolyimides are useful for the utilities discussed abovefor the polyimides.

The invention provides new monomers, oligomers, prepolymers and thecorresponding addition polyimides prepared therefrom. The monomers,oligomers and prepolymers are prepared by reacting the tetracarboxylicacids or derivatives of formulae (3) or (4), or the precursorcondensation product of the tetracarboxylic acids or derivatives offormulae (3) or (4) and the diamines of formula (5), with reactiveend-capping compounds such as vinyl aromatic anhydrides, nadic acids orderivatives thereof such as anhydrides or acid-esters, maleicanhydrides, aromatic ethynyl amines, or benzocyclobutene amines.

The monomers, oligomers and prepolymers are useful for adhesivecompositions, coating compositions, laminate varnish compositions, andcomposite matrix resin compositions. They may be reacted by additionpolymerization reactions to provide addition polyimides which are usefulfor coatings, laminates and composites.

One class of addition-type polyimide prepolymers may be characterized ashaving the following structure: ##STR15## wherein n is 1 to 5, R is adivalent organic radical as defined above, A is the tetravalent organicradical of formula (2), R_(a) is ##STR16## R_(b) is hydrogen, halogenpreferably fluorine, or lower (C₁ -C₃) alkyl preferably methyl, R_(c) is##STR17## Z is --(CH₂)_(t) --, t is 0 to 4, R_(d) is H or R_(c), andR_(e) is H or CH₃.

Preferably, R_(b) is hydrogen, R_(d) is hydrogen, n is 1 or 2, and t is8 or 1.

Preferably, R_(a) is ##STR18##

Generally speaking, this class of prepolymers may be prepared byreacting dicarboxylic acids, wherein the carboxyl groups are linked toadjacent carbon atoms, or derivatives thereof such as acid-esters oranhydrides, with the condensation product of the diamines of formula (5)and the tetracarboxylic acids or derivatives of formulae (3) or (4). Thepreferred end-capping compounds are vinyl-substituted ortho-phthalicacid anhydrides, nadic acid anhydrides and maleic acid anhydrides.

The diamine may be condensed first with the dianhydride and then theend-capping agent may be reacted with this intermediate condensationproduct. Alternatively, the diamine may be reacted with a mixture of thedianhydride and end-capping agent. The molar ratio of the diamine todianhydride must be sufficient to provide terminal amino groups at theends of the intermediate product for the purpose of reacting the productwith the end-capping agent. Generally, the molar ratios of diamine todianhydride will range from about 2:1 to about 4:3. The preferreddiamines are the 6F-44, 6F-33, BDAF, ODA, mPDA and pPDA.

The preparation of bismaleimides prepolymers and the correspondingaddition polyimides is generally shown in U.S. Pat. No. 4,173,700 toGreen et al., which is incorporated herein by reference. Thebismaleimides of the present invention may be characterized as havingthe structure: ##STR19## wherein n is 1 to 5, and R, A, and R_(b) arethe radicals as defined above. Preferably, R_(b) is hydrogen orfluorine, and n is 1 or 2. The preferred end-capping agents are maleicanhydride and difluoromaleic anhydride.

The preparation of bisnadimide prepolymers and the correspondingaddition polyimides is generally shown in U.S. Pat. No. 3,528,950 toHyman, which is incorporated herein by reference. The bisnadimides ofthe present invention may be characterized as having the structure:##STR20## wherein n is 1 to 5, and R, A, R_(b) and R_(d) are radicals asdefined above. Preferably, R_(b) is hydrogen or methyl, R_(d) ishydrogen, and n is 1 or 2. The preferred end-capping agent is5-norbornene-2,3-dicarboxylic acid anhydride.

Another method of preparing addition polyimides and polyimide prepregsusing nadic acid compounds is disclosed in U.S. Pat. No. 4,233,258 toSt. Clair, U.S. Pat. No. 4,281,102 to St. Clair et al., and Johnston etal., "A Mechanistic Study of Polyimide Formation from Diester-Diacids,"Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 25, pp.2175-2183 (1987), which are incorporated herein by reference. Accordingto this approach a diamine, a nadic acid-ester, and a tetracarboxylicdiacid-diester are dissolved in a lower alkyl alcohol such as a methanolor ethanol. The nadic acid-ester and tetracarboxylic diacid-diester maybe made by refluxing stoichiometric amounts of the nadic anhydride andtetracarboxylic dianhydride with excess alcohol such as ethanol. Theresulting solution is cooled to room temperature and the diamine is thenadded. The homogeneous mixture may then be used for prepregging ontofibers. The polymerization proceeds through two steps. The first stepinvolves heating to cause imidization (120-230° C.) to occur resultingin limited chain extension to form low molecular weight norboreneend-capped oligomers. In the second step, the norborene endcaps arecrosslinked by heating to higher temperatures (275°-325° C.) Becausethis final reaction occurs without the release of volatile materials,high quality void-free composites may be fabricated. Typically, thesolvents used in this type of system have been methanol and ethanol.However, it has been found that is is advantageous to use propyleneglycol methyl ether (PGME) as a solvent in this system. By using PGME,certain environmental hazards associated with the handling and disposalof solvents such as methanol and ethanol are avoided. The monomerreactants may be dissolved in up to about a 50 weight percent solutionusing PGME as a solvent.

The following examples are illustrative of prepolymers and additionpolyimides of this invention:

EXAMPLE 9

A four-necked flask fitted with a stirrer and maintained under anitrogen atmosphere is charged with 4.88 g (0.011 moles) of 6F-44, 3.81g (0.005moles) of l2F-DA , 90 ml of toluene and 10 ml of DMF. 1.08 g(0.011 moles) of maleic anhydride is added while stirring is continued.After 1 hour of stirring, 6.6 g of acetic anhydride and 0.5 g of sodiumacetate is added and the mixture is stirred for an additional 1 hour.The mixture is then heated to 50° C. for 8 hours. The reaction productis then precipitated in an ice-water mixture, filtered, washed severaltimes with water and dried overnight in a vacuum oven at 90° C.,yielding a bismaleimide oligomeric material.

1.0 g of the bismaleimide oligomeric material is dissolved in 3.0 ml ofNMP. The solution is spread on a glass plate to obtain a uniform film.The plate is dried in an air oven first at 90° C. for one hour and thenat 270° C. for one hour to remove the solvent and cure the oligomericmaterial.

EXAMPLE 10

A 3-neck flask purged with nitrogen and fitted with a condenser,thermometer, and stirrer is charged with 4.88 gms (0.011 moles) of 6F-44and 20 g of NMP under a nitrogen atmosphere. The mixture is stirred toobtain a clear solution. To the clear solution, 3.81 g (0.005 moles) of12F-DA is added while stirring is continued. 1.86 g (0.011 moles) ofcis-5-norbornene-endo-2,3-dicarboxylic acid anhydride (97% pure)(hereinafter "Nadic Anhydride") is then added also under continuousstirring. After charging with 24.45 g of NMP, the reaction mixture isstirred overnight at room temperature, resulting in a nadic-terminatedpolyamic acid.

To 65 g of the polyamic acid solution, 16.72 g of acetic anhydride and1.67 g of 3-picoline is added. The reaction mixture is stirred at roomtemperature for about six hours. The resulting nadic-terminatedoligomeric material is precipitated in methanol, isolated by filtration,washed with fresh methanol, and dried overnight in a vacuum oven at 85°C.

1.0 g of the nadic-terminated oligomeric material is dissolved in 3.0 mlof NMP. The solution is spread on a glass plate to obtain a uniformfilm. The plate is dried in an air oven first at 90° C. for one hour andthen at 270° C. for one hour to remove the solvent and cure theoligomeric material.

Another class of addition-type polyimide prepolymers may becharacterized as having the following structure: ##STR21## wherein n is0 to 4, preferably n is 0 or 1, R_(g) is ##STR22## R_(h) is H or##STR23## preferably H or --C₆ H₅, R_(i) is H, --O--C₆ H₅ or --O--C₆ H₄--SO₂ --C₆ H₅, preferably H, W is --O--, --S--, --SO₂ --, --CO--, --CH₂--, --C(CH₃)₂ --or --C(CF₃)₂ --, and t

is 0 to 4, preferably t is 0.

This class of prepolymers may be prepared by reacting end-capping amineswith tetracarboxylic acids or derivatives of formulae (3) or (4) or withintermediate compounds having terminal anhydride, diacid, or acid-estergroups. The intermediates are obtained by reacting excess molar amountsof tetracarboxylic acids or derivatives of formulae (3) or (4) withdiamines of formula (5). Generally, the molar ratios of dianhydride todiamine will range from 2:1 to 4:3. The intermediates are then reactedwith end-capping amines. Alternatively, the dianhydride may be reactedwith a mixture of the diamine and end-capping agent. The preferreddiamines are 6F-44, 6F-33, BDAF, ODA, mPDA and pPDA.

The preferred end-capping amines are 4-aminobenzocyclobutene,aminoarylacetylenes, and phenylacetylenearylamines.

The preparation of bisbenzocyclobutene substituted imide oligomers andthe corresponding addition polyimides is generally shown in Tan andArnold, "Benzocyclobutene in Polymer Synthesis I. Homopolymerization ofBisbenzocyclobutene Aromatic Imides to Form High-Temperature ResistantThermosetting Resins," Journal of Polymer Science, Polymer ChemistryEdition, Vol 26, pp. 18-19, (1988), which is incorporated herein byreference. The benzocyclobutene substituted imide oligomers of thepresent invention may be characterized as having the structure:##STR24## wherein n is 0 to 4, and R and A are as defined above.Preferably, n is 0 or 1.

The preparation of acetylene terminated imide oligomers and thecorresponding addition polyimides is generally shown in U.S. Pat. No.4,276,407 to Bilow et al. and PCT Publication No. WO 81/01293, Bilow etal., entitled "Acetylene Terminated Imide Oligomers Having ImprovedSolubilities and Lower Melting Points," which are incorporated herein byreference. The acetylene and phenylacetylene terminated imide oligomersof the present invention may be characterized as having the structure:##STR25## wherein n is 0 to 4, t is 0 to 4, and R, A, R_(h), and W aredefined as above. Preferably, n is 0 or 1, and t is 0.

Suitable end capping amines having terminal acetylene orphenylacetylenyl groups are those having the structure: ##STR26##wherein t is 0 to 4, preferably t is 0, and R_(h) and W are as definedabove. The preferred acetyleneamine is 3-aminophenylacetylene and thepreferred phenylacetylenylamine is 1-amino-3-phenylacetylenyl-benzene.

The preparation of benzocyclobutene-alkyne imide monomers and thecorresponding addition polyimides is generally shown in U.S. Pat. No.4,675,370 to Tan et al., which is incorporated herein by reference. Thebenzocyclobutene-alkyne monomers and oligomers of the present inventionmay be characterized as having the structure: ##STR27## wherein n is 0to 4, t is 9 to 4, R_(h) is hydrogen or phenyl, preferably R_(h) isphenyl, and R, A and W are as defined above. Preferably, n is 0, and tis 0.

The following examples are illustrative of imide oligomers and additionpolyimides of this invention:

EXAMPLE 11

A solution 8.38 g (0.011 moles) of 12F-DA in 75 ml of NMP at 50° C. ischarged into a three-necked flask equipped with stirrer under a nitrogenatmosphere. After stirring for 30 minutes, a solution of 0.0225 moles of4-aminobenzocyclobutene in 10 ml of NMP is added all at once. 75 ml oftoluene is then added and the reaction mixture is refluxed (at about143° C.) for 12 hours employing a Dean-Stark trap to remove the water.The solvent is distilled off using a mild vacuum. A residue remainswhich is precipitated using ethanol. A benzocyclobutene-terminatedmonomer product is obtained which is washed several times with ethanoland dried overnight in a vacuum oven at 90° C.

1.0 g of the benzocyclobutene-terminated monomer is dissolved in 3.0 mlof NMP. The solution is spread on a glass plate to obtain a uniformfilm. The plate is dried in an air oven first at 90° C. for one hour andthen at 270° C. for one hour to remove the solvent and cure the monomer.

EXAMPLE 12

A solution of 3.34 g (0.01 moles) of 6F-44 in 50 ml of NMP is addeddropwise to a solution of 16 g (0.021 moles) of 12F-DA in 75 ml of NMPat 50° C. in a three-necked flask equipped with stirrer under a nitrogenatmosphere. After heating the reaction contents at 50° C. for 30minutes, a solution of 3.6325 g (0.0225 moles) of 3-aminophenylacetylenein 10 ml of NMP is added all at once. 75 ml of toluene is then added andthe reaction mixture is refluxed (at about l43° C.) for 12 hoursemploying a Dean-Stark trap to remove the water. The solvent isdistilled off using a mild vacuum. A brown oily residue remains which isprecipitated using ethanol. A brown colored product is obtained which iswashed several times with ethanol and dried overnight in a vacuum ovenat 90° C.

1.0 g of the acetylene-terminated oligomeric material is dissolved in3.0 ml of NMP. The solution is spread on a glass plate to obtain auniform film. The plate is dried in an air oven first at 90° C. for onehour and then at 270° C. for one hour to remove the solvent and cure themonomer.

The invention provides copolymers prepared by reacting the acetylene orphenylacetylene terminated oligomers of formula (14) with other knownacetylene or phenylacetylene terminated monomers and oligomers. Variousacetylene terminated oligomers are described in, for example, U.S. Pat.Nos. 4,100,138 and 4,276,407 to Bilow et al., which are incorporatedherein by reference. U.S. Pat. No. 4,100,138 also describes thecopolymerization of acetylene terminated polyimide oligomers withdiethynylbenzene. Arylether compounds having terminal phenylethynylgroups are described in U.S. Pat. No. 4,513,131 to Reinhardt et al.,which is incorporated herein by reference.

The invention further provides compositions of component (A) comprisingknown polymides or copolyimides such as those described in U.S. Pat.Nos. 3,342,774 to Hoegger; 3,356,648 to Rogers; 3,424,718 to Angelo;3,649,601 to Critchley et al.; 3,926,913 to Jones et al.; 3,959,350 toRogers; 4,111,906 to Jones et al.; 4,477,648 to Jones et al.; 4,535,101to Lee et al.; 4,595,548 to St. Clair et al.; 4,603,061 to St. Clair etal.; and 4,612,361 to Peters; which are herein incorporated byreference; or a polyimide of formula (1); or mixtures thereof; andcomponent (B) comprising an addition-type polyimide monomer, oligomer orprepolymer of formulae (9), (10), (11), (12), (13), (14) or (16). Inanother aspect, the invention provides compositions wherein component(A) is a polyimide of formula (1) and wherein component (B) is a knownaddition-type polyimide monomer, oligomer or prepolymer such as thosedescribed in U.S. Pat. Nos. 4,173,700 to Green et al.; 3,528,950 toHyman, 4,233,258 to St. Clair, 4,281,102 to St. Clair et al.; 4,276,407to Bilow et al.; 4,675,370 to Tan et al.; the Tan and Arnold publicationreferred to above; and PCT Publication No. WO 81/01293, Bilow et al.;all of which are incorporated herein by reference. The compositions areuseful for producing films, composites and as matrix resins. When thecompositions are cured, the component (B) material is polymerizedforming interpenetrating networks or semi-interpenetrating networkswhich physically bond the molecules of the component (A) polymer in thenetwork.

Preferably, component (A) is present in the composition in the range offrom about 90 to about 10, more preferably from about 80 to about 20,percent by weight of the total combined weight of components (A) and(B). Preferably, component (B) is present in the composition in therange of from about 10 to about 90, more preferably from about 20 toabout 80, percent by weight of the total combined weight of components(A) and (B).

The following examples are illustrative of the invention:

EXAMPLE 13

A composition is prepared by dissolving 1.0 g of SIXEF-44™ polyimide (apolyimide prepared from 6F-DA dianhydride and 6F-44 diamine), availablefrom Hoechst Celanese Corporation, Somerville, N.J., and 1.0 g ofbismaleimide oligomeric material prepared according to Example 9 in 10.0ml of NMP. The solution is spread over a glass plate to obtain a uniformfilm. The coated plate is dried in an air oven first at 90° C. for onehour and then at 270° C. for one hour to evaporate the residual solventand to cause cross-linking of the bismaleimide oligomeric material.

EXAMPLE 14

A composition is prepared by dissolving 1.0 g of SIXEF-44™ polyimide (apolyimide prepared from 6F-DA dianhydride and 6F-44 diamine), availablefrom Hoechst Celanese Corporation, Somerville, N.J., and 1.0 g ofnadic-terminated oligomeric material prepared according to Example 10 in10.0 ml of NMP. The solution is spread over a glass plate to obtain auniform film. The coated plate is dried in an air oven first at 90° C.for one hour and then at 270° C. for one hour to evaporate the residualsolvent and to cause cross-linking of the bisnadimide oligmericmaterial.

EXAMPLE 15

A composition is prepared by dissolving 1.0 g of SIXEF-44™ polyimide (apolyimide prepared from 6F-DA dianhydride and 6F-44 diamine), availablefrom Hoechst Celanese Corporation, Somerville, N.J., and 1.0 g ofacetylene-terminated oligomer prepared according to Example 12 in 10.0ml of NMP. The solution is spread over a glass plate to obtain a uniformfilm. The coated plate is dried in an air oven first at 90° C. for onehour and then at 270° C. for one hour to evaporate the residual solventand to cause cross-linking of the acetylene-terminated oligomer.

The invention further provides bis(amino-imide) compounds useful ascuring agents for polyfunctional epoxy resins. The bis(amino-imide)compounds of the present invention may be characterized as having thestructure: ##STR28## wherein n is 1 to 5, and R and A are radicals asdefined above. Preferably n is 1 or 2.

The bis(amino-imide) compounds may be prepared by known methods such asthose described in U.S. Pat. No. 4,244,857 to Serafini et al., which isincorporated herein by reference. They are conveniently prepared byreacting of formulae (3) or (4) with diamines of formula (5). The molarratio of diamine to dianhydride is preferably in the range of about 2:1to about 4:3.

The following example is illustrative of the preparation of thebis(amino-imide) compounds of the present invention:

EXAMPLE 16

A 3-neck flask purged with nitrogen and fitted with a condenser,thermometer, and stirrer is charged with 6.68 g (0.02 moles) of 6F-44and 20 g of NMP under a nitrogen atmosphere. The mixture is stirred toobtain a clear solution. 7.62 g (0.01 moles) of 12F-DA is added whilestirring is continued. After the addition is completed, the solution isstirred at room temperature under nitrogen for two hours. The solutionis then refluxed for two hours. After cooling, the solution is pouredinto 400 ml of distilled water with vigorous stirring. The precipitateis filtered, washed with water, and dried overnight in a vacuum oven at85° C. to yield the bisaminoimide.

The invention also provides epoxy resin compositions. The epoxy resincomposition comprises a polyfunctional epoxy resin and a curing agent.The curing agent may be a bis(amino-imide) compound of formula (17).

The polyfunctional epoxy resins to which the invention relates arewidely known and described in the literature and need not be redescribedherein.

The ratio by weight of epoxy resin to curing agent is preferably in therange of from about 10:90 to about 90:10, more preferably of from about20:80 to about 80:20.

The compositions of epoxy resins and curing agent are used to impregnatefibers, such as carbon, boron and glass, and may also be filled withparticulate fillers to provide high performance fiber reinforced plasticarticles or filled epoxy resins which are used to fabricate a widevariety of molded articles. The preparation of epoxy resin compositionsand molded articles therefrom is described in the above-referenced U.S.Pat. No. 4,244,857 to Serafini et al. and in D. A. Scola, "Synthesis andCharacterization of Bisimide Amines and Bisimide Amine-Cured EpoxyResins," Polymer Composites, Vol. 4, No. 3, pp. 154-161, (July, 1983),which is incorporated herein by reference. The compositions may also beused as adhesives.

The following example is illustrative of the invention:

EXAMPLE 17

A solution of 16 g of the bis(amino-imide) compound prepared in Example16 in 10 g of BLO solvent is mixed with 10 g of a bisphenol A diepoxide(Interez 510) at room temperature. The mixture is cast on a glass plateand heated at 110° C. for 3 hours resulting in a cured film.

The solvent soluble polyimides and their polyamic acid precursors of theinvention may be used in the preparation of photosensitive compositionsand processed by conventional techniques to provide thermally stablerelief patterns. These photosensitive compositions are useful in manyapplications such as photopolymerizable varnishes or protective layerssuch as passivation overcoat films, planarization layers inmicroelectronic circuits, insulating layers for multi-layered hybridcircuits and as photoresists that provide relief structures of gooddefinition on substrates such as silicon chips, polymeric films andmetal plates. They provide polymeric layers or relief structures thatpossess high thermal and radiation stability, excellent mechanicalproperties and high insulating properties. In other applications such asprinting plates, the tough mechanical properties of thephotopolymerizable compositions of the invention provide a means to makeprinting plates having the capability of giving long printing runs.

In one form, the photosensitive compositions of the invention comprise amixture of a solvent soluble polyimide of the invention, aphotoinitiator and a photopolymerizable compound containing at least twoterminal ethylenically unsaturated groups.

Suitable photopolymerizable material comprises an additionpolymerizable, non-gaseous (boiling temperature above 100° C. at normalatmospheric pressure), ethylenically-unsatrurated compound containing atleast two terminal ethylenic groups, and being capable of forming a highmolecular weight polymer by free radical initiated, chain propagatingaddition polymerization. Illustrative examples include tetraethyleneglycol dimethacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol propane triacrylate, polyethyleneglycol (200) or (600) diacrylate, diethylene glycol dimethacrylate,pentaerythritol tetraacrylate, pentaerythritol triacrylate,1,6-hexanediol dimethacrylate, dipentaerythritolmonohydroxypentaacrylate, ethoxylated bisphenol A dimethacrylate,tripropylene glycol diacrylate, tris(2-hydroxyethyl)isocyanurate,trimethylacrylate tris(2-hydroxyethyl)triacrylate, glycerol diacrylate,glycerol triacrylate, hexamethylene diamine, diacrylamide and mixturesthereof.

Suitable photoinitiators useful in the practice of the invention aredisclosed in U.S. Pat. Nos. 4,464,457; 4,465,758 and 4,619,998 which areincorporated herein by reference. A large number of substances can beused in the mixture of the present invention as polymerizationintitiators which can be activated by radiation, particularly actiniclight. Examples are benzoin and its derivatives,trichloromethyl-s-triazines,1,3-bistrichloromethyl-5-(para-biphenyl)triazine-2,4,6;1,3-bistrichloromethyl-5-(para-stilbenyl)triazine-2,4,6; acridinederivatives, for example, 9-phenylacridine, 9-p-methoxyphenylacridine,9-acetylaminoacridine and benz(l)-acridine. Other examples are phenazinederivatives, for example, 9,10-dimethylbenz(a)phenazine and10-methoxybenz(a)phenazine, quinoxaline derivatives, for example,6,4',4"-trimethoxy-2,3-diphenylquinoxaline and4',4"-dimethoxy2,3-diphenyl-5-azaquinoxaline. The initiators aregenerally employed in the present invention in an amount of 0.01 to 20,preferably 0.05 to 10 percent by weight, relative to the non-volatilecomponents of the mixture.

The mixture according to the present invention generally contains 20 to90, preferably 30 to 80, percent by weight of solvent soluble polyimideand 80 to 10, preferably 70 to 20, percent by weight of polymerizablecompounds, relative in each case to the total amount of non-volatileethylenically unsaturated monomer and polyimide components.

The mixture can contain, as further conventional components,polymerization inhibitors, oxygen scavengers, hydrogen donors,sensitometric regulators, dyes, pigments, plasticizers and thermallyactivatable crosslinking agents.

It is generally advantageous to substantially isolate the compositionsof the present invention from the influence of atmospheric oxygen duringphotopolymerization. If the composition is used in the form of a thincopying layer, it is recommended that a suitable cover film with a lowpermeability to oxygen be applied to the layer.

Leuco bases of triarylmethane dyes that are suitable for use in thepresent invention include those of Crystal Violet, Victoria Blue BH,Victoria Pure Blue BOH, Methyl Violet, and Acilan Violet S.

Suitable actinic radiation to which the composition according to thepresent invention is sensitive is any electromagnetic radiation whoseenergy is sufficient to initiate polymerization. Visible and ultrvioletlight, x-rays and electron radiation are particularly suitable Laserradiation in the visible and UV range can also be used. Short-wavelengthvisible and near-UV light is preferred.

The photosensitve compositions of the invention may be employed insolution which can be applied to a substrate by any conventinal method,such as roller coating, dipping, spraying, whirling and spin coating.They may be prepared into and used as dry films as is taught in U.S.Pat. No. 3,469,982 to Celeste which is incorporated herein by reference.

Suitable substrates include silicon, aluminum, glass, polymeric resinboards and films, silicon dioxide, doped silicon dioxide nitride,tantalum, copper, polysilicone ceramics and aluminum/copper mixtures

Suitable application solvents include N-methyl- pyrrolidone,dimethylformamide, γ-butyrolactone, acetone, diglyme, tetrahydrofuran,propylene glycol methyl ether, propylene glycol methyl ether acetate,and mixtures thereof The photosensitive composition after exposure maybe developed by any suitable organic solvent, e.g., γ-butyrolactone,toluene, propylene glycol methyl ether/toluene,N-methylpyrrolidone/toluene, acetone/water mixtures etc.

The following examples are illustrative of the photosensitivecompositions of the invention:

EXAMPLE 18

A photosensitive composition is prepared using the solvent solublepolyimide of Example 2:

    ______________________________________                                        Example 2 Polyimide   4.0    grams                                            Pentaerythritol triacrylate                                                                         1.5    grams                                            1,3-bistrichloromethyl-5-                                                                           0.1    grams                                            (p-stilbenyl)triazine-2,4,6                                                   Dye                   0.03   grams                                            Diglyme/BLO (50/50)   16.0   grams                                            ______________________________________                                    

The resulting photosensitive compostion is filtered under pressure andis roller coated on an anodized aluminum plate. The coated plate ispre-baked at 90° C. for 3 minutes to obtain a resist film. The film isthen overcoated with a polyvinyl alcohol protective layer (10% in water)and prebaked at 90° C. for 2 minutes. The film is then covered with aphotomask having a striped pattern so that the film and the photomaskare in tight contact. The film is exposed through an Addalux vacuumprinter (2KW, photopolymer lamp/UV broad band radiation) for anirradiation time range of 300 sec. After the irradiation, the coating isfirst rinsed with hot water to remove the polyvinyl alcohol overcoat,then is developed with a mixed solution of 4 volume of BLO and 1 volumeof toluene and rinsed with n-hexane to give a negative image.

Other developers include a mixture of toluene/NMP (9:1) andacetone/water (7:3).

EXAMPLE 19

A photosensitive composition is prepared and processed in accordancewith the procedure of Example 18 using the solvent soluble polyimide ofExample 3:

    ______________________________________                                        Example 3 Polyimide   2.0    grams                                            Pentaerythritol triacrylate                                                                         0.4    grams                                            1,3-bistrichloromethyl-5-                                                                           0.3    grams                                            (p-stilbenyl)triazine-2,4,6                                                   Diglyme/BLO (50/50)   15.0   grams                                            ______________________________________                                    

Similarly, the polyamic acid precursors of the polyimides of theinvention may be substituted for the fully imidized polymers of theforgoing examples 18 and 19. However, after the image is developed, thefilm is converted to a polyimide by baking at 275°-350° C. for 0.5 to 3hours.

The forgoing examples illustrate the use of the polymers of theinvention as negative acting resists. However, they may also be used toproduce positive acting compositions as illustrated by the teachings ofU.S. Pat. No. 4,093,461 which are incorporated herein by reference. Inthese compositions, the polyamic acid precursor is mixed with aphotosensitive orthoquinone or naphthoquinone diazide and processed inthe conventional manner to produce a positive relief structure.

What is claimed is:
 1. A polyimide polymer having groups of thestructure: ##STR29## wherein n is the number of repeating groups, A is##STR30## and R is a divalent organic radical.
 2. The polyamide of claim1, wherein R is selected from the group consisting of ##STR31## whereinR₂ is a carbon-carbon bond, --O--, --S--, --SO₂ --, --CO--, --(CH₂)_(r)--, ##STR32## --O--(CH₂ --CH₂ --O)_(r) --, --O--(CF₂)_(s) --O--,##STR33## wherein R₃ is a carbon-carbon bond, --S--, --SO₂ --, --CO--,--CH₂ --, --C₂ H₄ --, ##STR34## R₄ is halogen, hydroxy, lower (C₁ -C₆)alkyl or lower (C₁ -C₆) alkoxy, m is 0 to 2, r is 1 to 4, and s is 1 to5.
 3. Polyamide-acid polymeric material having groups of the structure:##STR35## wherein n is the number of repeating groups, A is ##STR36## Ris a divalent organic radical, and R' is hydrogen or a monovalentorganic radical.
 4. The polyamide-acid polymeric material of claim 3,wherein R is selected from the group consisting of ##STR37## wherein R₂is a carbon-carbon bond, --O--, --S--, --SO₂ --, --CO--, --(CH₂)_(r) --,##STR38## --O--(CH₂ --CH₂ --O)_(r) --, --O--(CF₂)_(s) --O--, ##STR39##wherein R₃ is a carbon-carbon bond, --S--, --SO₂ --, --CO--, --CH₂ --,--C₂ H₄ --, ##STR40## R₄ is halogen, hydroxy, lower (C₁ -C₆) alkyl orlower (C₁ -C₆) alkoxy, m is 0 to 2, r is 1 to 4, and s is 1 to
 5. 5.Polyamide-acid polymeric material prepared by reacting a dianhydridehaving the formula: ##STR41## and at least one diamine having theformula:

    H.sub.2 N--R--NH.sub.2

wherein R is a divalent organic radical.
 6. The polyamide-acid polymericmaterial of claim 5, wherein the diamine is selected from the groupconsisting of:m-phenylene diamine; p-phenylene diamine;1,3-bis(4-aminophenyl) propane; 2,2-bis(4-aminophenyl) propane;4,4'-diamino-diphenyl methane; 1,2-bis(4-aminophenyl) ethane;1,1-bis(4-aminophenyl) ethane; 2,2'-diamino-diethyl sulfide;bis(4-aminophenyl) sulfide; 2,4'-diamino-diphenyl sulfide;bis(3-aminophenyl) sulfone; bis(4-aminophenyl) sulfone;4,4'-diamino-dibenzyl sulfoxide; bis(4-aminophenyl) ether;bis(3-aminophenyl) ether; bis(4-aminophenyl) diethyl silane;bis(4-aminophenyl) diphenyl silane; bis(4-aminophenyl) ethyl phosphineoxide; bis(4-aminophenyl) phenyl phosphine oxide;bis(4-aminophenyl)-N-phenylamine; bis(4-aminophenyl)-N-methylamine; 1.2-diamino-naphthalene;1,4-diamino-naphthalene; 1,5-diamino-naphthalene;1,6-diamino-naphthalene; 1,7-diamino-naphthalene;1,8-diamino-naphthalene; 2,3-diamino-naphthalene;2,6-diamino-naphthalene; 1,4-diamino-2-methyl-naphthalene;1,5-diamino-2-methyl-naphthalene; 1,3-diamino-2-phenyl-naphthalene;4,4'-diamino-biphenyl; 3,3'-diamino-biphenyl;3,3'-dichloro-4,4'-diamino-biphenyl;3,3'-dimethyl-4,4'-diamino-biphenyl;3,4'-dimethyl-4,3'-diamino-biphenyl;3,3'-dimethoxy-4,4'-diamino-biphenyl; 4,4'-bis(4-aminophenoxy)-biphenyl;2,4-diamino-toluene; 5-diamino-toluene;3,3'-butoxy-4,4'-diamino-biphenyl; 2.6-diamino-toluene;3,5-diamino-toluene; 1,3-diamino-2,5-dichloro-benzene;1,4-diamino-2,5-dichloro-benzene; 1-methoxy-2,4-diamino-benzene;1,4-diamino-2-methoxy-5-methyl-benzene;1,4-diamino-2,3,5,6-tetramethyl-benzene;1,4-bis(2-methyl-4-amino-pentyl)-benzene;1,4-bis(1,1-dimethyl-5-amino-pentyl)-benzene;1,4-bis(4-aminophenoxy)-benzene; o-xylylene diamine; m-xylylene diamine;p-xylylene diamine; 3,3'-diamino-benzophenone;4,4'-diamino-benzophenone; 2,6-diamino-pyridine; 3,5-diamino-pyridine;1,3-diamino-adamantane; 3,3'-diamino-1,1'-diadamantane;bis(4-amino-cyclohexyl) methane; 1,5-diamino-pentane;1,6-diamino-hexane; 1,7-diamino-heptane; 1,8-diamino-octane;1,9-diamino-nonane; 1,10-diamino-decane; 1.7-diamino-3-methyl-heptane;1,7-diamino-4,4-dimethyl-heptane;2,11-diamino-dodecane; 1,3-bis(3-aminopropoxy) ethane;1,3-diamino-2,2-dimethyl-propane; 1,6-diamino-3-methoxy-hexane;1,6-diamino-2,5-dimethyl-hexane; 1,7-diamino-2,5-dimethyl-heptane;1,9-diamino-5-methyl-nonane; 1,4-diamino-cyclohexane;2,5-diamino-1,3,4-oxadiazole; N-(3-aminophenyl)-4-aminobenzamide;4-aminophenyl-3-aminobenzoate; 2,2-bis(4-aminophenyl) hexafluoropropane;2,2-bis(3-aminophenyl) hexafluoropropane;2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane;2,2-bis[4-(2-chloro-4-aminophenoxy)phenyl] hexafluoropropane;1,1-bis(4-aminophenyl)-l-phenyl-2,2,2-trifluoroethane;1,1-bis[4-(4-aminophenoxy)phenyl]-l-phenyl-2,2,2-trifluoroethane;1,4-bis(3-aminophenyl)buta-l-ene-3-yne;1,3-bis(3-aminophenyl)hexafluoropropane; and1,5-bis(3-aminophenyl)decafluoropentane.
 7. Copolyamide-acid polymericmaterial prepared by reacting a dianhydride having the formula:##STR42## at least one diamine having the formula:

    H.sub.2 N--R--NH.sub.2

wherein R is a divalent organic radical; and at least one dianhydridehaving the formula: ##STR43## wherein B is a tetravalent organic radicalhaving at least 4 carbon atoms.
 8. An addition-type polyimide prepolymerhaving the structure: ##STR44## wherein n is 1 to 5, R is a divalentorganic radical,A is ##STR45## R_(b) is hydrogen, halogen or lower (C₁-C₃) alkyl, R_(c) is ##STR46## Z is --(CH₂)_(t) --, R_(d) is H or R_(c),R_(e) is H or CH₃, and t is 0 to
 4. 9. A bisnadimide prepolymer havingthe structure: ##STR47## wherein n is 1 to 5, R is a tetravalent organicradical, andA is ##STR48##
 10. A bismaleimide prepolymer having thestructure: ##STR49## wherein n is 1 to 5, R is a divalent organicradical,A is ##STR50## and R_(b) is hydrogen, halogen or lower (C₁ -C₃)alkyl.
 11. An addition-type polyimide prepolymer having the structure:##STR51## wherein n is 0 to 4, R is a divalent organic radical,A is##STR52## R_(g) is ##STR53## R_(h) is H or ##STR54## R_(i) is H, --O--C₆H₅ or --O--C₆ H₄ --SO₂ --C₆ H₅, W is --O--, --S--, --SO₂ --, --CO--,--CH₂ --, --C(CH₃)₂ -- or --(CF₃)₂ --, and t is 0 to
 4. 12. An acetylenesubstituted imide oligomer having the structure: ##STR55## wherein n is0 to 4, t is 0 to 4,R is a divalent organic radical, A is ##STR56##R_(h) is H or ##STR57## R_(i) is H, --O--C₆ H₅ or --O--C₆ H₄ --SO₂ --C₆H₅, and W is --O--, --S--, --SO₂ --, --CO--, --CH₂ --, --C(CH₃)₂ -- or--C(CF₃)₂ --.
 13. A benzocyclobutene substituted imide oligomer havingthe structure: ##STR58## wherein n is 0 to 4, R is a divalent organicradical, andA is ##STR59##
 14. An imide oligomer having the structure:##STR60## wherein n is 0 to 4, R is a divalent organic radical, andA is##STR61## R_(h) is H or ##STR62## R_(i) is H, --O--C₆ H₅ or --O--C₆ H₄--SO₂ --C₆ H₅, W is --O--, --S--, --SO₂ --, --CO--, --CH₂ --, --C(CH₃)₂-- or --CF₃)₂ --, and t is 0 to
 4. 15. A photosensitive compositioncomprising a polyimide according to claim 1, a photopolymerizablecompound containing at least two terminal ethylenically unsaturatedgroups and a photoinitiator.
 16. A photosensitive composition comprisinga polyamide-acid polymeric material according to claim 3, aphotopolymerizable compound containing at least two terminalethylenically unsaturated groups and a photoinitiator.
 17. Aphotosensitive composition comprising a polyamide-acid polymericmaterial according to claim 3 and a light sensitive orthoquinone diazideor ortho naphthoquinone diazide.
 18. A copolyimide polymer prepared froma copolyamide polymeric material of claim
 7. 19. A polyimide polymerprepared from a polyimide prepolymer of claim
 8. 20. A polyimide polymerprepared from a bisnadimide prepolymer of claim
 9. 21. A polyimidepolymer prepared from a bismaleimide prepolymer of claim
 10. 22. Apolyimide polymer prepared from a polyimide prepolymer of claim
 11. 23.A polyimide polymer prepared from an imide oligomer of claim
 12. 24. Apolyimide polymer prepared from an imide oligomer of claim
 13. 25. Apolyimide polymer prepared from an imide oligomer of claim
 14. 26. Anarticle fabricated from a polyimide polymer of claim
 1. 27. An articlefabricated from a polyamide-acid polymeric material of claim
 3. 28. Anarticle fabricated from a polyamide-acid polyameric material of claim 5.29. An article fabricated from a copolyamide-acid polymeric material ofclaim
 7. 30. An article fabricated from a copolyimide of claim
 18. 31.An article fabricated from a polyimide prepolymer of claim
 8. 32. Anarticle fabricated from a polyimide prepolymer of claim
 9. 33. Anarticle fabricated from a bismaleimide prepolymer of claim
 10. 34. Anarticle fabricated from a polyimide prepolymer of claim
 11. 35. Anarticle fabricated from an imide oligomer of claim
 12. 36. An articlefabricated from an imide oligomer of claim
 13. 37. An article fabricatedfrom an imide oligomer of claim
 14. 38. A polymer composition comprisinga solvent soluble thermoplastic polyimide polymer and a thermosetpolyimide polymer prepared from an addition-type polyimide prepolymer ofclaim
 8. 39. A polymer composition comprising a solvent solublethermoplastic polyimide polymer and a thermoset polyimide polymerprepared from an addition-type polyimide prepolymer of claim
 11. 40. Apolymer composition comprising a polyimide polymer of claim 1 and athermoset polyimide polymer prepared from an addition-type polyimidemonomer, oligomer or prepolymer having a reactive endcap group of thestructure: ##STR63## wherein R_(b) is hydrogen, halogen or lower (C₁-C₃)alkyl, R_(c) is ##STR64## R_(d) is H or R_(c), R_(e) is H orCH₃,R_(h) is H or ##STR65## R_(i) is H, --O--C₆ H₅ or --O--C₆ H₄ --SO₂--C₆ H₅, Y is --O--, --S--, --SO₂ --, --CO--, --Ch₂ --, --C(CH₃)₂ -- or--(CF₃)₂ --, Z is --(CH₂)_(t) --, and t is 0 to 4.